Water-insoluble azo dyestuffs



United States Patent 3,522,235 WATER-INSOLUBLE AZO DYESTUFFS Thomas Douglas Baron and Brian Ribbons Fishwick, Manchester, England, assignors to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Continuation-impart of application Ser. No. 480,119, Aug. 16, 1965. This application Sept. 19, 1968, Ser. No. 761,001 Claims priority, application Great Britain, Aug. 26, 1964, 34,944/ 64 Int. Cl. C07c 107/06; C09b 29/24 U.S. Cl. 260-207 Claims ABSTRACT OF THE DISCLOSURE Water-insoluble azo dyestuffs derived from a diazo component oftheb enzene series and a coupling component of the formula III-X-Y II wherein X is CO, SO or COO Y is lower alkyl, chloro lower alkyl, bromo lower alkyl,

lower alkoxy lower alkyl, cyclohexyl, benzyl, phenyl, tolyl or methoxyphenyl;

Z is hydrogen, lower alkyl or lower alkoxy;

R is lower alkyl;

W and W are each lower alkylene; and

n is an integer of from 1 to 10; and the use of the said dyestuffs for colouring synthetic textile materials.

wherein A is the radical of a diazo component of the benzene series which is directly attached to the azo group through a carbon atom of said benzene ring;

X is selected from the group consisting of CO,

SO;, and

Y is selected from the group consisting of lower alkyl, chloro lower alkyl, bromo lower alkyl, lower alkoxy lower alkyl, cyclohexyl, benzyl, phenyl, tolyl and methoxyphenyl;

3,522,235 Patented July 28, 1970 Z is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy;

R is a lower alkyl radical;

W and W each independently represent lower alkylene radicals; and

n is a positive integer of from 1 to 10.

Throughout this specification the terms lower alkyl and lower alkoxy are used to denote alkyl and alkoxy radicals respectively containing from 1 to 4 carbon atoms. The term lower alkylene radical is used to denote an alkylene radical containing from 1 to 6 carbon atoms.

As examples of the lower alkyl radicals represented by Z and R there may be mentioned ethyl, propyl, butyl and, preferably, methyl radicals; and as examples of the lower alkoxy radicals represented by Z there may be mentioned ethoxy, propoxy, butoxy and, preferably, methoxy radicals.

As examples of the lower alkylene radicals represented by W and W there may be mentioned methylene, propylene, trimethylene, tetramethylene, uzfi-dimethylethylene, a:'y-dirnethyltrimethylene, hexarnethylene and, preferably, ethylene radicals.

As examples of the radicals represented by Y there may be mentioned lower alkyl such as methyl, ethyl, n-propyl and n-butyl, chloro lower alkyl such as fi-chloroethyl and B- or 'y-chloro-mpropyl, bromo lower alkyl such as B-bromoethyl, and lower alkoxy lower alkyl such as ,B-(methoxy or ethoxy) ethyl and B- or 'y-(methoxy or ethoxy) n-propyl.

It is however preferred that X represents the CO group and Y a lower alkyl radical, so that the group -XY preferably represents an acyl radical of the formula CO-Y wherein Y is a lower alkyl radical, preferably the methyl radical.

It is preferred that the integer represented by n is an integer of from 1 to 3, and, above all, n preferably represents 1. When n has a value of from 2 to 10 then it is not necessary that each radical represented by W has the same value; thus for example when n is 2 one W can be the ethylene radical and the other W the trimethylene radical.

The radical of a diazo component of the benzene series represented by A is preferably a phenyl radical which may contain up to four substituents selected from the group consisting of lower alkyl, lower alkoxy, chlorine, bromine, nitro, lower alkyl sulphonyl, [i-cyanoethylsulphonyl, trifluoromethyl, cyano, thiocyano, carbonamido (CONH sulphonamido (SO NH N-lower alkyl sulphonamido, N:N-di(lower alkyl) sulphonamido, N-lower alkyl carbonamido, N:N-di(lower alkyl) carbonamido, N-phenyl sulphonamido, N-phenyl carbonamido, carbo lower alkoxy (lower alkoxycarbonyl), bromo lower alkoxy carbonyl, chloro lower alkoxy carbonyl and acetoxy lower alkoxycarbonyl.

As specific examples of such substituents which may be present on the phenyl radical represented by A there may be mentioned methyl, methoxy, ethoxy, ethylsulfonyl, n-propylsulphonyl, N-methylsulphonamido, N- ethylsulphonamido, N-n-butylsulphonamido, N-methyl- N ethylsulphonamido, N:N diethylsulphonamido, N- methylcarbonamido, N:N-diethylcarbonamido, carbomethoxy, carboethoxy, fi-bromoethoxycarbonyl, fl-chloroethoxycarbonyl and -acetoxy-n-propoxycarbonyl.

Above all it is preferred that A represents a radical of the formula:

wherein T is selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, nitro, lower alkylsulphonyl, fl-cyanoethylsulphonyl, trichloromethyl, cyano, thiocyano, carbonamido, sulphonamido, N-lower alkyl carbonarnido, N:N-di(lower alkyl)carbonamido, N-lower alkyl sulphonamido, N:N-di(lower alkyl) sulphonamido, N-phenyl carbonamido, N- phenyl-sulphonamido, carbo lower alkoxy, bromo lower alkoxy carbonyl, acetoxy lower alkyl carbonyl and chloro lower alkoxy carbonyl:

T is selected from the group consisting of hydrogen, cyano, nitro, chlorine, bromine and carbo lower alkoxy; and

T is selected from the group consisting of hydrogen,

chlorine, bromine, nitro and cyano.

Preferably A is a radical of the formula:

wherein U is selected from the group consisting of hydrogen, nitro,

chlorine, bromine, cyano, lower alkyl sulphonyl, trifluoromethyl and carbo lower alkoxy; and

V is selected from the group consisting of hydrogen,

chlorine, bromine and nitro.

Above all A is a radical selected from the group consisting of 2:4-dinitro-6-chlorophenyl, 2:4-dinitro-6-bromophenyl and 2:4: 6-trinitrophenyl.

As specific examples of groups of the formula:

there may be mentioned B-(tV-methoxyethoxycarbonyl) ethyl, fl-(,B'-ethoxyethoxycarbonyl)ethyl, ,8 ('y-methoxybutoxycarbonyl)ethyl, B '-methoxpropoxycarbonyl) ethyl, B (/3'-butoxyethylcarbonyl)ethyl, 6 methoxyethoxycarbonyhmethyl, [3 (13 ethoxethoxycarbonyl) butyl, 18-(B-isopropoxyethoxycarbonyl)ethyl, p-methoxymethoxycarbonyl)ethyl, 8-[fi'-(B" methoxethoxy)ethoxycarbonylJethyl and ,8 {,8'[fi"-( 3' methoxyethoxy) ethoxy] ethoxycarb onyl} ethyl.

The azo dyestuifs of the invention can be obtained by diazotising a primary amine of the benzene series of the formula ANH and coupling the resulting diazo compound With a coupling component of the formula wherein A, R, X, Y, Z, W W and n have the meanings stated above, the primary amine and coupling component being free from carboxylic acid or sulphonic acid groups.

This reaction can be conveniently brought out by adding an aqueous solution or suspension of the diazotised primary amine to a solution of the coupling component in a dilute aqueous solution of an acid such as hydrochloric acid, stirring the resulting mixture, preferably at a pH between 3 and 7, to effect formation of the monoazo dyestuff, and finally isolating the monoazo dyestulf by conventional methods.

The diazotised primary amines used in this reaction can be any diazotised primary amines of the benzene series. As specific examples of primary amines of the benzene series there may be mentioned aniline, mor p-toluidine, o-, mor p-anisidine, o-, mor p-chloroaniline, o-, mor p-bromoaniline, o-, mor p-nitroaniline, 2:5-dichloroaniline, 2:4-dinitroaniline, 2:4-dinitro-6-(chloro or bromo)aniline, 4-methanesulphonylaniline, 4-aminobenzotrifluoride, 4- or S-nitro-Z-toluidine, 4- or 5-nitro-2-anisidine, 4- or Sachloro-Z-anisidine, 4- or 5-chloro-2-toluidine, 4- or 5-bromo-2-anisidine, 2:6-di(chloroor br0mo)-4-nitroaniline, 2:4: 6-trinitroaniline, 2 4-dinitro6-carbomethoxy aniline, 2-amino-5-nitrobenzotrifluoride, 2:4-bis(methanesulphonyl)aniline, 2-(chloroor bromo-)-4-nitroaniline, methylanthranilate, 4- or 5-nitromethylanthranilate, 4- aminobenzamide, 2:6-di(chloroor bromo-)aniline-4- sulphonamide, 2:6-di(chloroor bromo)-4-methylsulphonylaniline, 2:5-di(chloroor bromo-)-4:6-dinitroaniline, 2-amino-3:5-dinitrobenzotrifluoride, 3-amino-2- (chloroor bromo-)-4: 6-dinitro-(to1uene or anisole), 3- amino-4-(chloroor bromo-)-2:6-dinitro-(toluene or anisole), 2- or 4-cyanoaniline, 4-nitro-2-cyanoaniline, 2:4- dinitro-6-cyanoaniline, 2-nitro-4-cyanoaniline, 2-chloro-4- cyanoaniline, 3-amino-2:4:6-trinitrotoluene, 2-(chloroor bronio-) 4 methylsulphonylaniline, 3 (chloroor bromo-)-4-thiocyanoaniline, Z-(chloroor bromo-)-4- sulphamylaniline, Z-amino 5 nitrophenylmethanesul phone, 2 amino 3:5-dinitrophenylmethylsulphone, 2- amino-3-(chloroor bromo-) 5 nitrophenylmethylsulphone, 2-sulphamyl-4-nitroaniline, 2-methylsulpharnyl-4- nitroaniline, 2-phenylsulphamyl-4-nitroaniline, 2-ethylsulphamyl-4-nitroaniline, Z-butylsulphamyl-4-nitroaniline, 2- dimethylsulphamyl-4 nitroaniline, 2 methylsulphamyl- 4:6-dinitroaniline, 2 methy1sulpharnyl-4-nitro-6-(chloroor bromo-)aniline, Z-phenylsulphamyl-4-nitroanil.ine, 4- carbonamidoaniline, methyl Z-amino 3 (chloroor bromo-)-5-nitrobenzoate, dimethyl Z-aminoterephthalate, and dimethyl Z-amino-S-nitroterephthalate.

The coupling components of Formula I can themselves be obtained by esterifying a compound of the formula:

with an alcohol of the formula: HO--(W -O) R wherein Z, X, Y, W W R and n have the meanings stated, or by esterifying a compound of the formula:

with an alcohol of the formula: HO(W --O) R, reducing the nitro group to a primary amino group, and finally acylating the primary amino group, so as to convert the NH group to a -NH.X.Y group.

As specific examples of the coupling components of Formula I there may be mentioned 2 methoxy-S-acetylamino [N-(fl'-methoxyethoxycarbonyl)ethyl]aniline, 3- acetylamino N-[,3-(;8'-ethoxyethoxycarbonyl)ethy1]aniline, 3 benzoylamino-N- 3-(;3'-ethoxyethoxycarbonyl) ethyl]aniline, 2-methoxy-5-acetylamino-N [B-(y-methoxybutoxycarbonyl)ethyl]aniline, Z-methoxy-S acetylarnino N- [,3-('y'methoxypropoxycarbonyl) ethyl] aniline, 2-methoxy-5-acetylamino-N {fl-[B'-(fl'-methoxyethoxy) ethoxycarbonyl]ethyl}aniline, Z-ethoxy-S-aeetylamino-N- 8-(,6'-methoxyethoxycarbonyl) -ethyl] aniline, Z-methyl- S-acetylamino N-[B-(fi methoxyethoxycarbonyl)ethyl] aniline, 2-ethoxy-5-acetylamino N [B-(;3'-ethoxyethoxycarbonyl)ethyl] aniline, 2 methoxy-S-propionylamino-N- 3- (B'-methoxyethoxycarbonyl ethyl] aniline, 2-tmethoxy- 5 benzoylamino N -(fi'-methoxyethoxycarbonyl) ethylJaniline, 2-methoxy-S-methylsulphonylamino-N-[B- (B-methoxyethoxycarbonyl)ethyl]aniline, Z-methoxy-S- chloroacetylamino N 8-(fi'-methoxyethoxycarbonyl)- ethyl] aniline, Z-methoxy-S-methoxyacetylamino N [,8- ,B'-methoxyethoXycarbony1)ethylJaniline and Z-methoxy- S-methoxycarbonylamino N [B-(fi-methoxyethoxycarbonyl)ethyl] aniline.

A preferred class of the dyestuffs of the invention comprises those dyestuffs wherein n has a value of from 1 to 3, and above all the dyestuffs wherein n has a value of 1.

A second preferred class of the dyestuffs of the invention comprises the dyestuffs of the formula:

comprises the dyestuffs of the formula:

/H AN=N N\ omom-ooo-omom-o-n NHCOYI wherein A, R, Y and Z have the meanings stated.

In these classes A preferably has the preferred values given above.

A fourth preferred class of the dyestuffs of the invention comprises the dyestuffs of the formula:

I IHOOY wherein A is 2:4dinitro-6-chlorophenyl, 2:4-dinitro-6- bromophenyl or 2:4:6-trinitrophenyl, R is lower alkyl, Z is lower alkoxy and Y is lower alkyl.

The monoazo dyestuffs, as hereinbefore defined, are valuable for colouring synthetic textile materials, for example cellulose acetate and cellulose triacetate textile materials, polyamide textile materials such as polyhexamethyleneadipamide textile materials, and preferably aromatic polyester textile materials such as polyethylene terephthalate textile materials. Such textile materials can be in the form of thread, yarn, or woven or knitted fabric.

Such textile materials can conveniently be coloured with the monoazo dyestuffs, as hereinbefore defined, my immersing the textile material in a dyebath comprising an aqueous dispersion of one or more of the said dyestuffs, which dyebath preferably contains a non-ionic, cationic and/or anionic surface-active agent, and thereafter heating the dyebath for a period at a suitable temperature. In the case of secondary cellulose acetate textile materials it is preferred to carry out the dyeing process at a temperature between 60 and 85 C.; in the case of cellulose triacetate or polyamide textile material it is preferred to carry out the dyeing process at 95 to 100 C.; in the case of aromatic polyester textile materials the dyeing process can either be carried out at a temperature between 90 and 100 C. preferably in the presence of a carrier such as diphenyl or o-hydroxydiphenyl, or at a temperature above 100 C., preferably at a temperature between 120 and 130 C., under superatmospheric pressure.

Alternatively the aqueous dispersion of the said monoazo dyestuff can be applied to the textile material by a padding or printing process, followed by heating or steaming of the textile material. In such processes it is preferred to incorporate a thickening agent, such as gum tragacanth, gum arabic, or sodium alginate, into the aqueous dispersion of the said monoazo dyestuff.

At the conclusion of the colouring process it is preferred to give the coloured textile material a rinse in water or a brief soaping treatment before finally drying the coloured textile material. In the case of aromatic polyester textile materials it is also preferred to subject the coloured textile material to a treatment in an alkaline aqueous solution of sodium hydrosulphite before the soaping treatment in order to remove loosely attached dyestulf from the surface of the textile material.

The monoazo dyestuffs have excellent aflinity and building up properties on synthetic textile materials, and in particular on aromatic polyester textile materials, so enabling deep shades to be obtained. The resulting colorations which range in shade from yellow to blue, have excellent fastness to light, to wet treatments, and, in particular, to dry heat treatments such as those carried out at high temperatures during pleating operations.

If desired the dyestuffs of the invention can be applied to synthetic textile materials in conjunction with other disperse dyes.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

EXAMPLE 1 2.62 parts of 2:4-dinitro-6-bromoaniline are added during 30 minutes to a solution of nitrosylsulphuric acid at 25 C., which is prepared by dissolving 0.7 part of sodium nitrite in 8 parts of sulphuric acid, and the resulting mixture is then stirred for 2 hours at 55 to 60 C. The resulting solution of the diazo compound is added to a solution of 3.1 parts of 2-methoxy-5-acetylamino- [,8-(fi'-methoxyethoxycarbonyl) ethyl] aniline in a mixture of 60 parts of acetone and 60 parts of a 0.2 M aqueous solution of hydrochloric acid at 5 C., and the mixture is stirred for a further 30 minutes. The dyestuif which is precipitated is then filtered off, washed with water and dried.

When dispersed in aqueous medium the dyestuif dyes polyethylene terephthalate textile materials in navy blue shades which have excellent fastness to light and to dry heat treatments.

The Z-methoxy-S-acetylamino N [p3 (/3-methoxyethoxycarbonyl)ethyl] aniline used in the above example was itself obtained by condensing 2-methoxy-5-nitroaniline with acrylic acid, esterifying the resulting 2- methoxy-S-nitro-N-(B-carboxyethyl)aniline with [3 methoxyethanol in the presence of sulphuric acid, reducing the nitro group to an amino group and finally acylating this amino group by treatment with one molecular proportion of acetic anhydride in pyridine at a temperature of 20 C.

EXAMPLE 2 2.41 parts of 2:4-dinitro-6-(methoxycarbonyl)aniline are added to a solution of nitrosylsulphuric acid, which is prepared by dissolving 0.7 part of sodium nitrite in 8 parts of sulphuric acid at 25 C., and the resulting mixture is stirred for 2 hours at 5 C. The resulting solution of the diazo compound is added to a solution of 3.24 parts of 2 methoxy S-acetylamino-N-[18-(B'-methoxyethoxycarbonyl)propyl]aniline in a mixture of 60 parts of acetone and 60 parts of a 0.2 N aqueous solution of hydrochloric acid, the temperature of the mixture being maintained at 5 C. by external cooling. The mixture is stirred for a further 30 minutes at 5 C., and the precipitated dyestuif is then filtered off, washed with water and dried.

When dispersed in aqueous medium the dyestuif dyes polyethyleneterephthalate textile materials in navy blue shades which have excellent fastness to light and to dry heat treatments.

The 2-methoxy-5-acetylamino N [fl-(B'-methoxyethoxycarbonyl)propyl]aniline used in the above example was itself obtained by condensing o-anisidine with methacrylic acid, nitrating the product With a mixture of nitric and sulphuric acids, esterifying the resulting 2-methoxy-5-nitro-N-(fi-carboxypropyl) aniline with 3 methoxyethanol in the presence of sulphuric acid, reducing the nitro group to an amino group, and finally converting the primary amino group to an acetylamino group.

EXAMPLE 3 2.62 parts of 2:4-dinitro-6-bromoaniline are diazotised as described in Example 1, and the resulting solution of 8 the diazo compound is added to a solution of 3.24 parts mixture is stirred for 30 minutes. A solution of 10 parts of 2 ethoxy d-acet ylamino-N- [fl-(B'-methoxyethoxycarof sodium acetate in 50 parts of water is then added and bonyl)ethyl]aml1ne in 100 parts of a 0.2 N aqueous soluthe precipitated dyestufi is filtered off, washed with water tion of hydrochloric acid, the temperature of the mixture nd dried,

being maintained between and C. by external cool- When dispersed in aqueous medium the dyestuif dyes ing. The mixture is stoved for a further 30 minutes at the polyethylene terephthalate textile materials in deep bluishsame temperature, and the precipitated dyestuff is then red shades having excellent fastness to dry heat treat- -filtered off, washed with water and dried. merits.

When dispersed in aqueous medium the dyestulf dy s The following table gives further examples of the waterpolyethyleneterephthalate textile materials in navy blue 10 insoluble azo d e tuff of th i nti h vi th forshades which possess excellent fastness to light and to dry mula: heat treatments. Z

The coupling component used in this example was obl tained in a similar manner to the coupling component of Example 1 except that 2-ethoxy-5-nitroaniline was used as the starting material instead of 2-methoxy-5-nitroani- )uR line.

EXAMPLE 4 A solution of 1.74 parts of 2-chloro-4-nitroaniline in a the y s of which have the values given in t sp mixture of 15 parts of acetic acid and 10 parts of a contive columns of the table, and the shades f dyeihgs centrated aqueous solution of hydrochloric acid is cooled tained from the said dyestufis are given in the last column to 5 C., a solution of 0.7 part of sodium nitrite in 10 of the table. parts of water is added with stirring, and the mixture The said dyestuffs may be obtained by methods similar stirred for 15 minutes. The mixture so obtained is added to those described in Examples 1 to 4 by diazotising the to a solution of 2.8 parts of 3-acetylamino-N-[fl-(B'-methappropriate amines of the formula: A--NH and couoxyethoxycarbonyl)ethyl]aniline in 100 parts of a 0.2 N pling the resulting diazo compounds with the appropriate aqueous solution of hydrochloric acid at 5 C., and the coupling components of Formula 1.

Ex. A X Y Z W l W 2 n R Shade 5 2:4diuitro-6-ehlorophenyl C0- Methyl Methoxy Ethylene Ethylene 1 Methyl Grgelenish navy ue. 6 2:4-dinitto-6-bromophenyl- Navy blue.

d Do. Do. D0. D0. Greenish navy blue.

Do. Do. Do. Navy blue. 1 do Reddish navy blue. do .110 a-Methyl- 1 do Navy blue.

ethylene. 18..- 2z4-dinitro-6-ch10rophenyl. Tetrarnethyldo 1 .d0 Do.

ene. 19 2:4-dinitro-6-bromophenyl. do .d0 mB-Dimethdo 1 do Do.

ylethylene. 20"... 2:4-dinitro-6-chlorophenyl. CO r1o do Hexamethyldo 1 do Do 6118. 21 do OO ..do do Ethylene"... Hexamethyl- 1 do Do.

ene. 22 2:4-dinitro-6-bromo- CO do do do a-Methyltri- 1 do Do.

. methylene.

-do do do Ethylene l iso-Propyl Do. do do do l ma-Dilneth- Do.

ylethyl. do rlo "do Trimethylenm 1 Methyl Grlelenish navy ue. do do do Ethylene Do. do do .-do Trimethylene- Do.

do do do Ethylene Do. 29 :4-dini o yanophenyl. do Greenish-blue. 30 2-cl1l0ro4-nit1'0-6-(carbo- OO do do d0 .JlO o Violet.

methoxy)phenyl. 31 2:4-dlnitr0-6(carbo- -CO-- do ..do do "do Navy blue.

methoxy)pheny1. 32..." 2:4-dinitro-6w-(methoxy) -CO do d0 do .do Do.

ethoxyearbonyflphenyl. 33 2-bromo-4-nitro-6-cyano- --CO do do clo d0 1 do Greenish navy phenyl. blue. 34"". 2:6-dibromo-4-nitro- CO d0 .d0 do d0 1 do Reddish-violet.

phenyl.

35 2:G-dichloroknitrophenyl. Do.

36... 2:5-dichlor0-4zG-dinitro- Reddish navy phenyl.

37. 2:4-dinitro-6-trlflu01'o- Grecnish navy methylphenyl. blue.

38..- Z-trifluoromethyM-nitro- Bluish red.

phenyl.

39 2-cyano-4-nitrophenyl. Violet.

40.. 2-methylsulphonyl-4- Reddish-violet.

nitrophenyl.

41 2:4-dinitro-6-methylsul- 1 do Greenish navy phonylphenyl. blue.

42"... 2-bromo-4-nitro-6-methyh 1 do Bluish violet.

sulphonylphenyl.

43 2:5-di(carbomethoxy)-4- 1 do Bluish red.

nitrophenyl.

44... 2:4-dinitro-6-chlorophenyl 1 do Ggeienlsh navy Ex. A X Y Z W W 1 do Greenish navy blue. n-Butyl do ..do do 1 do Navy blue.

Phenyl "do do d 1 do Ggeienish navy ue. Oyclohexyl do "do do 1 do Do. 2-methoxyd0 d0 do 1 do Do.

phenyl. 4-methyldo do do. 1 -do Do.

phenyl. 66 do .2 C00- Methyl .do do do 1 do Navyblue. 57..-" 2:4-dinitro-6-chlorophenyl OOO Ethyl dn dn dn do Ggeienlsh navy ue. 58 do iso-Propyl do do dn 1 do Navy blue. 69 do Phenyl. do do dn 1 do Gaeenish navy ue. 60..- 2:4-dinitro-6-bromo- Methyl do do do 1 do Violet.

G1 yl 1 do Do. 2: nitro-fi-chlorophenyl. d 1 do Do. 63 2:4-dinitro-6-bromo- 1 do Navy blue.

64 o Do.

methyl. 65 do Chloromethyl do Do. 66. 4-nitrophenyl Methyl Hydrogen Scarlet.

4-chlorophenyl d henyl 2: 5-diehloro4-nitrophenyl- 2:4-bis(methylsulphonyl) phenyl.

72 2:4-dicyanophenyl 73. 2-cyano-4-nitrophenyl 74 2-1nethylsu1phonyl-4- nitrophenyl.

75 2-caI11'bomethoxy-4-nitro- Orange. Reddish-yellow. Red.

Scarlet.

t1 lnltrophenyL nitro-G-bromophen lethy ehlorophenyl. 83.-- 2:4-dinitro-3-methoxy-6- chlorophenyl. 84 4-nifiro2icarbamoyl- CO- do Hydrogen d0 -do 1 do Bluish-red.

p eny 85 2:6-}(liich10ro-4-sulphamyl- CO- dn do do d 1 do Red.

p en 8(i 2-brhomo-4thiocyano- CO- ..do do do 1 do Reddish orange.

p en 87..-" 2-n-butylsulphamyl-4- CO do do do do 1 do Navy blue.

dinitrophenyl. 88 zdiethylsulphamyllzfi- CO dn do rln dn dinitrophenyl. 89. 2-phenylsulphamyl-4z6- -CO do do dinitrophenyl. 90 2-phenylsulphonyl-4g6- CO rln dn dn do dinitrophenyl. 9l Zphenylcarbamoyl-k -CO do Hydrogen .-do do nitrophenyl. 92 2-n-propylcarbamoyl-4:6- CO- do Methoxy do do dinitrophenyl. 93 2-dimethylcarbamoyl-4a6- C0 do .1 dn

dinitrophenyl. 94 2-B-cyanoethylsulphonyl- CO-- do do 4-nitrophenyl. 95..-" Q-fl-ehloroethoxycarbonyl- CO do do do dn e-nitrophenyl.

96 Z-fl-bromoethoxycarbonyl- 4:6-dinitropl1enyl.

97 2-y-acetoxypropoxycarbonyl-4:6-dinitrophenyl.

99 2:4: 6-tribromophenyL 1o0 2=4 10l 2:3 :5tetrachlorophenyl 102 2;4-dinitro-dbromophenyl- Ethoxy..

Methoxy The coupling components used in Examples 78 to 81 The alcohols of the formula HO-(C H -O) CH were themselves obtained by condensing 2-methoxy-5- where t has the values given above were themselves obnitroaniline with acrylic acid, esterifying the resulting 2- tained as follows: methoxy 5 nitro-N-(B-carboxyethyl) analine with the api=4 (methoxy tetraglycol) u-methoxy-B-(p'-hydroxypropriate alcohol of the formula HO--(C H -O) CH 70 ethoXy)-ethane was reacted with thionyl chloride and the wherein t has a value of 4, 5, 6 or 10, in the presence of resulting compound of the formula CH (OC H C1 was sulphuric acid, reducing the nitro group to an amino reacted with the monosodium salt of ethylenediglycol. group, and finally acylating the amino group by treatment t=5 (methoxypentaglycol): The compound of the forwith one molecular proportion of acetic anhydride in mula CH (OC H Cl was reacted with the monosodium pyridine at a temperature of 20 C. 75 salt of ethylene triglycol.

1 1 t=6 (methoxyhexa-glycol): CH (OC H OH was reacted with thionyl chloridea nd the resulting A represents a phenyl radical which may contain up to four substituents selected from the group consisting of lower alkyl, lower alkoxy, chlorine, bromine, nitro, lower alkylsulphonyl, B-cyano-ethylsulphonyl, trifluoromethyl, cyano, thiocyano, carhonamido (CONH sulphonamido (SO NH N-lower alkyl sulphonamido, N:N-di(lower alkyl) sulphonamido, N-lower alkyl carbonamido, NzN-di- (lower alkyl)carbonamido, N-phenylsulphonamido, N-phenylcarbonamido, carbo lower alkoxy (lower alkoxycarbonyl), bromo lower alkoxycarbonyl, chloro lower alkoxycarbonyl and acetoxy lower alkoxycarbonyl;

X is selected from the group consisting of CO,

SO and wherein Y is selected from the group consisting of lower alkyl,

chloro lower alkyl, bromo lower alkyl, lower alkoxy lower alkyl, cyclohexyl, benzyl, pheny, tolyl and methoxy-phenyl;

Z is selected from the group consisting of hydrogen,

lower alkyl and lower alkoxy;

R is a lower alkyl radical;

W and W each independently represent lower alkylene radicals; and

n is a positive integer of from 1 to 3.

2. Water-insoluble monoazo dyestufis as claimed in claim 1 wherein A is a radical of the formula:

wherein T is selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, nitro, lower alkylsulphonyl, fl-cyanoethylsulphonyl, trifluoromethyl, cyano, thiocyano, carbonamido, sulphonamido, N-lower alkyl carbonamide, N:N-di(lower alkyl)carbonamido, N lower alkylsulphonarnido, N:N di (lower alkyl)sulphonamido, N-phenylcar- 12 bonamide, N-phenylsulphonamido, carbo lower bromo lower alkoxycarbonyl, chloro lower alkoxycarbonyl and acetoxy lower alkoxycarbonyl;

T is selected from the group consisting of hydrogen, cyano, nitro, chlorine, bromine and carbo lower alkoxy; and

T is selected from the group consisting of hydrogen,

chlorine, bromine, nitro and cyano.

3. Water-insoluble monoazo dyestuffs as claimed in claim 1 wherein A is a radical of the formula:

wherein U is selected from the group consisting of hydrogen, nitro, chlorine, bromine, cyano, lower alky1sulphonyl trifluoromethyl and carbo lower alkoxy; and

V is selected from the group consisting of hydrogen,

chlorine, bromine and nitro. 4. The water-insoluble monoazo dyestulfs as claimed in claim 1 which are of the formula:

wherein A is selected from the group consisting of 2:4-dinitro-fi-chlorophenyl, 2:4-dinitro-6-bromophenyl and 2: 4: 6-trinitrophenyl;

Y is lower alkyl;

R is lower alkyl;

W and W each represent lower alkylene; and

Z is selected from the group consisting of hydrogen,

lower alkyl and lower alkoxy.

5. The water-insoluble monoazo dyestuffs as claimed in claim 1 which are of the formula:

/H A -N=N -N\ CHzCHzCOOCHZCHflOR NHC 0Y wherein A is selected from the group consisting of 2:4-dinitro- 6 chlorophenyl, 2:4 dinitro-6-bromophenyl and 2: 4: 6-trinitrophenyl;

Z is lower alkoxy;

Y is lower alkyl; and

R is lower alkyl.

References Cited UNITED STATES PATENTS 3,097,198 7/1963 Fishwick et al. 260207.1

OTHER REFERENCES 1,069,313 11/1959 Germany.

CHARLES B. PARKER, Primary Examiner C. F. WARREN, Assistant Examiner US. Cl. X.R. 

